Fluctuating Dynamics of Nanoscale Chemical Oscillations: Theory and Experiments

Barroo, Cédric; Decker, Yannick De; Bocarmé, Thierry Visart de; Gaspard, Pierre

doi:10.1021/acs.jpclett.5b00850

Cited by 19 publications

(26 citation statements)

References 39 publications

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“…For a typical chemical oscillator this analysis predicts the lower limit of the number of molecules to be between 10 and 100. This result could be validated in recent experimental studies on the oscillatory NO 2 + H 2 reaction on nano-sized Pt tips [6]. Here, the product of the correlation time of the oscillations and the variance of the period of the oscillations was shown to be constant.…”

Section: Introductionsupporting

confidence: 75%

“…9 together with the theoretical predicted curve [6] given by: which has a slope of −1 and an intercept of ln(1/2π 2 ) ≈ −2.98. The data were obtained for two different U values and system sizes that all have Gaussian distributions of the period.…”

Section: Valuementioning

confidence: 66%

“…For an electrochemical oscillator, the latter can be roughly estimated to be 1 to 2 times the value of Ω min , assuming that a typical oscillator has two to three types of adsorbed species with average coverages of 0.3 -0. Despite the strong dependence of the quality of a nonlinear oscillator on the characteristics of the limit cycle in the macroscopic system, theory predicts that in the low-noise limit where the chemical master equation reduces to a Fokker-Planck equation the product of the relative correlation time τ / T and the relative variance of the first return times σ 2 / T 2 should be equal to 1/2π 2 [6]. For an electrochemical nanoscale system, the time-dependence of the rate coefficients k hampers the derivation of a Fokker-Plank equation, and in fact makes it impossible to follow the same lines as for the a chemical system [19].…”

Section: Valuementioning

confidence: 99%

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Destructive impact of molecular noise on nanoscale electrochemical oscillators

Cosi

Krischer

2017

Eur. Phys. J. Spec. Top.

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Abstract. We study the loss of coherence of electrochemical oscillations on meso-and nanosized electrodes with numeric simulations of the electrochemical master equation for a prototypical electrochemical oscillator, the hydrogen peroxide reduction on Pt electrodes in the presence of halides. On nanoelectrodes, the electrode potential changes whenever a stochastic electron-transfer event takes place. Electrochemical reaction rate coefficients depend exponentially on the electrode potential and become thus fluctuating quantities as well. Therefore, also the transition rates between system states become time-dependent which constitutes a fundamental difference to purely chemical nanoscale oscillators. Three implications are demonstrated: (a) oscillations and steady states shift in phase space with decreasing system size, thereby also decreasing considerably the oscillating parameter regions; (b) the minimal number of molecules necessary to support correlated oscillations is more than 10 times as large as for nanoscale chemical oscillators; (c) the relation between correlation time and variance of the period of the oscillations predicted for chemical oscillators in the weak noise limit is only fulfilled in a very restricted parameter range for the electrochemical nano-oscillator.

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Section: Introductionsupporting

confidence: 75%

Section: Valuementioning

confidence: 66%

Section: Valuementioning

confidence: 99%

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Destructive impact of molecular noise on nanoscale electrochemical oscillators

Cosi

Krischer

2017

Eur. Phys. J. Spec. Top.

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“…The unique possibility to image reaction dynamics make them a fruitful technique towards the understanding of fundamental phenomena occurring at the surface of catalytic particles. For example, processes such as nonlinear behaviour, surface explosions [142] or oscillations [143][144][145][146], but also reconstructions, morphology-reactivity relationship and diffusion [147] can be studied with these techniques. Moreover, these techniques can be coupled with mass spectrometry and are known as Pulsed Field Desorption Mass Spectrometry (PFDMS), or sometimes referred as the 1-Dimensional Atom Probe (1DAP) [140,148].…”

Section: Field Emission Microscopy Fem/field Ion Microscopy Fimmentioning

confidence: 99%

Dynamic Processes on Gold-Based Catalysts Followed by Environmental Microscopies

et al. 2017

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Abstract:Since the early discovery of the catalytic activity of gold at low temperature, there has been a growing interest in Au and Au-based catalysis for a new class of applications. The complexity of the catalysts currently used ranges from single crystal to 3D structured materials. To improve the efficiency of such catalysts, a better understanding of the catalytic process is required, from both the kinetic and material viewpoints. The understanding of such processes can be achieved using environmental imaging techniques allowing the observation of catalytic processes under reaction conditions, so as to study the systems in conditions as close as possible to industrial conditions. This review focuses on the description of catalytic processes occurring on Au-based catalysts with selected in situ imaging techniques, i.e., PEEM/LEEM, FIM/FEM and E-TEM, allowing a wide range of pressure and material complexity to be covered. These techniques, among others, are applied to unravel the presence of spatiotemporal behaviours, study mass transport and phase separation, determine activation energies of elementary steps, observe the morphological changes of supported nanoparticles, and finally correlate the surface composition with the catalytic reactivity.

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“…This result represents yet another indication that the Fokker-Planck approach is relevant for studying chemical reactions at the nanoscale. [25]). The dashed line is the best linear fit of the data.…”

Section: C(t)mentioning

confidence: 99%

Nonlinear Dynamics of Reactive Nanosystems: Theory and Experiments

Decker

Bullara

Barroo

et al. 2015

Bottom-Up Self-Organization in Supramolecular Soft Matter

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Reactive systems are known to give birth to complex spatiotemporal phenomena, when they are maintained far enough from their equilibrium state. There are literally hundreds of experimental evidences showing the emergence of such self-organized behaviors at the macroscopic scale. Examples include the appearance of regular oscillations of concentration in both space and time, the formation of stationary spatial organization of reactants and products, and the emergence of spatiotemporal chaos, to cite but a few examples.The theoretical understanding of these phenomena can be considered as being well established. Chemical reactions play a central role in the appearance of complex behaviors because they are nonlinear processes. Indeed, the rates of reactions are typically polynomials of the concentrations and moreover include constants that depend exponentially on the temperature. Because of this, the equations ruling the spatiotemporal development of chemical reactions, which often take the form of reaction-diffusion equations, admit complicated (and even sometimes multiple) solutions. The number and the type of solutions change abruptly for some precise combinations of the parameters of the system, which are known as bifurcation points. This feature explains why new dynamical behaviors are observed only whenever a

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Fluctuating Dynamics of Nanoscale Chemical Oscillations: Theory and Experiments

Cited by 19 publications

References 39 publications

Destructive impact of molecular noise on nanoscale electrochemical oscillators

Destructive impact of molecular noise on nanoscale electrochemical oscillators

Dynamic Processes on Gold-Based Catalysts Followed by Environmental Microscopies

Nonlinear Dynamics of Reactive Nanosystems: Theory and Experiments

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